Thiocyano aliphatic ethers of hydroxydihydronordicyclopentadiene



Patented Feb. 26, 1946 PATENT orFic THIOCYANO ALIPHATIG ETHERS OF HY- I DROXYDIHYDRONORDICYCLOI E N T A DI- Herman A. Bruson, Philadelphia, Pa.,.a ssignor to The Resinous Products & Chemical Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application September 12, 1944,

Serial N0. 553,801

7 Claims. (01. 260-454) This invention relates to new thiocyano aliphatic ethers of hydroxydihydronordicyclopenta diene. These ethers have the general formula ;I

wherein CmHis represents the dihydronordicyclopentadienyl group, A is an alkylene group having a chain of at least two carbon atoms, and n is zero or a whole number.

This application is a continuation-in-part of my copending application Serial No. 476,640; filed February 20, 1943, wherein there is disclosed the reaction of alcohols with polycyclopentadienes having two double bonds per molecule in the presence of acidic condensing agents. In this reaction, the alcohol is added to one of these double bonds of the endomethylene cycle with a simultaneous rearrangement of this cycle to an endoethylene cyclopentano system having a cyclopenteno group attached thereto. The new. ring system has been named "norpolycyclopentadiene generically and nordicyclopentadiene for the specific system from dicyclopentadiene. The alcohols corresponding thereto may be termed hydroxydihydronorpolycyclopentadiene and hydroxydihydronordicyclopentadiene respectively. The ethers of the latter alcohol and thiccyano aliphatic alcohols are the subject matter claimed herein. a g

The reaction which occurs when a thiocyano aliphatic monohydric alcohol reacts with dicyclopentadiene may be represented as follows:

wherein C3H4 is a propenylene group which in conjunction with the. adjoining carbon atoms forms a cyclopenteno group..

Thiocyano alcohols, which correspond to the above general formula where n is one to three, have been set forth by applicant in application Serial No. 526,483, filed March 14, 1944, now Patent No. 2,372,809, April 3, 1945. .These are prepared by heating a polyalkylene halohydrin in water or an inert organic solvent at about 50 C. to about 150 C. with a salt of thiocyanic ammonium thiocyanate.

,Where thiccyano alcohols are not available and as an alternative method, the compounds of this invention may be prepared by first reacting a Typical alcohols which may be used in the above reactions are the following:

HOCHaCHzCI or the corresponding bromide HOCH(CHa) CHzCl or the corresponding bromide HOCH2CH2CH2C1 or the corresponding bromide HOCHzCHzCHzCHzCl orthe corresponding bromide HOCHzCI-IzOCHzCHzCl or the corresponding bromide HOCH2CH(CH3) OCH(CH3) CH2B1 HOCHzCHzOCHzCHzOCHzCHzCl HOCHzCHzCHzCHzBr HOCHzCHzOCHzCHzSCN HOCH2CH(CH3) OCH(CI-I3) CHzSCN HOCH2CH2CH2OCH2CH2CH2SCN HOCH2CH2OCH2CH2OCH2CH2SCN HOCHzCHzOCHzCHzOCHzCHaOCI-IzCHzSCN HOCH2CH2(OCH2CH2) nSCN where n is an integer up to 15 or more.

The following examples present details of some of the preferred ways of preparing the compounds 55 of this invention:

acid, such as sodium, potassium, calcium, lead or trample 1 To a stirred solution of 63 sramsof dicyclopentadiene and 60 grams of p-thiocyauoethoxyethanol at 60' .0.- there was added grams of boron trifiuorido-diethyl ether complex BB5.0(C:Hs) 2.

as a colorless oil boiling at l95-198 C./3 mm. having the following constants:

a 1.5251; d4 0.9415 Example 2 "To a stirred solution of 623 grams of p-chloroethoxyethanol and 9 grams of boron trifluoride at 95' Cethere was gradually added 695 grams of dicyclopentadiene during the course of forty-five The mixture was then stirred for nine at 90-1959v C., and finally worked up by with dilute soda solution and water, drydistilling in vacuo.

The ,e-chloroethoxy ethoxydihydronordicycloof the probable formula Hr ciomcHr-o-cmcm-o-ln- J: C I

distilled over'at l50-160 C./3-4 mm. as a colorless oil in a yield of 470 grams.

This product was then mixed with 212 grams of sodium thiocyanate, 198 grams of methyl isobutyl ketone, grams of p-ethoxyethanol, 1 gram of copper powder and 2 grams of sodium bromide andheatedwith stirring for 24 hours at 130 C. under reflux. The product was then washed with ;--wateranddistilledinvacuotoyield390srams of p thiocyanoethoxyethoxydihydronordicyclopentadiene boiling at 180-190 C. (1-2 mm.) havi sthesamephysicaland chemicalpropertiesas the product described in Example 1.

Example 3 To a stirred solution of 47.3 grams of trlmethylme chlorhydrln and 3 name of boron trifluol ether complex BF:.O(CH9): at 75- 85 C. there was gradually added during the course of twenty minutes '70 grams of dicyclopentadlene. The mixture was stirred and heated at 90' G. for three and one-quarter hours. The dark oil which was obtained was washed with dilute sodium hydroxide solutioraand then with water, dried. and in vacuo. The -chloropropyl etheg of hydroxydihydronordicyclopentadiene, distilled over at 1l0-120'f'CJ2 mm. as a colorless oil in a yield of 30 :ranis. Upon redist illation the pure compound boiled at 114-115 iii/1.5 mm.

On'e molecular-equivalent of the above comwlth 1.1 moles of powdered P taslium thiqcy nate and twice its we ht of meththe sulfuric acid had been added, the mixture was allowed to come to room temperature (28 C.) and then stirred with 132 grams of pure dicyclopentadiene. A gradual exothermal reaction set in during which the temperature rose to 75" C. within half an hour. After this had subsided the mixture was stirred at -95" C. for two and onequarter hours. The product was washed with water and the residual oil was taken up in toluene and made alkaline by the addition of calcium hydroxide. The product was filtered and the filtrate distilled under reduced pressure. The pchloroethoxydihydronordicyclopentadiene of the probable formula distilled over at -131 0J6 mm. as a colorless or faintly yellow oil in a yield of 125 grams. Upon redistillation it came over as a colorless oil :of pleasant odor boiling at 129-431 0.]? mm.

A mixture of 212.5 grams of the above p-chloroethoxydihydronordicyclopentadiene, 107 grams of methyl isobutyl ketone, 10 grams of p-ethoxyethanol, 0.5 gram of copper powder, 0.5 gram of sodium bromide and 116 grams of pure sodium thiocyanate was stirred at 132-148 C. for 24 hours. The product was then cooled, washed with water several times, filtered, dried, and distilled in vacuo. The p-thiocyanoethoxydihydronordicyclopentadiene of the probable formula:

N CB-CHsC r-O H E distilled over at -165 C./1-2 mm. as a colorlessoilinayieldof grams. Uponredistillation the pure compound was obtained as a colorless oil boiling at 147-149 C./1 mm.

In the same manner as in Example 4, p-chloropropyloxydihydronordicyclopentadiene,

yields the corresponding p-thiocyanopropyloxvdihydronordicyclopentadiene as a colorless oil having insecticidal properties.

The thiocyano aliphatic ethers of hydroxydihy dronordicyclopentadiene are high boiling liquids which are useful as softeners for gummy and resinous compositions. They are useful as toxicants in insecticidal compositions and may be used in lubricating oil compositions in giving better mm strensth, preventin corrosion, etc.

I claim:

1. As a new compound, a thiocyano aliphatic ether of hydroxydihydronordicyclopentadiene having the formula 3. p-Thiocyanoethoxyethoxydihydronordicyclopentadiene having the formula 4. As a new compound, a thiocyano aliphatic ether having the formula C1oH13OCH2CH2(O-CH2CH2) nSCN wherein n is a number from zero to three.

of hydroxydihydronordicyclopentadiene 2o 5. A method for preparing a thiocyano aliphatic ether of hydroxydihydronordicyclopentadiene which comprises adding together dicyclopentadiene and an aliphatic monohydric thiocyano alcohol in the presence of an acidic condensing agent with simultaneous molecular rearrangement.

6. A method for preparing a thiocyano aliphatic ether of hydroxydihydronordicyclopentadiene which comprises adding together dicyclopentadiene and an aliphatic monohydric thiocyano a1- cohol in the presence of a boron trifluoride catalyst with simultaneous molecular rearrangement.

7. A method for preparing wherein C1oH1: is the dihydronorclicyclopentadienyl group which comprises adding together dicyclopentadiene and p-thiocyanoethoxyethanol in the presence of a boron trifluoride catalyst with a simultaneous molecular rearrangement.

HERMAN .A. BRUSON. 

